Synthesis and Characterization of Homo- and Heteroleptic Neptunium(IV) Heteroarylalkenolate Complexes

Grödler, Dennis; Kaden, Peter; Sperling, Joseph M.; Rotermund, Brian M.; Scheibe, Benjamin; Beck, Nicholas B.; Lichtenberg, Andreas; Albrecht, Thomas E.; Mathur, Sanjay; Gericke, Robert

doi:10.1021/acs.inorgchem.4c04521

Title: Synthesis and Characterization of Homo- and Heteroleptic Neptunium(IV) Heteroarylalkenolate Complexes

Journal Article · 27 January 2025 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.4c04521 · OSTI ID:2507103

Grödler, Dennis ^[1];

^[1];

^[2];

^[2]; Scheibe, Benjamin ^[3];

^[2]; Lichtenberg, Andreas ^[4];

^[2];

^[4];

^[1]

Helmholtz-Zentrum Dresden-Rossendorf (Germany)
Colorado School of Mines, Golden, CO (United States)
Colorado School of Mines, Golden, CO (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
University of Cologne (Germany)

Heteroleptic An^IV (An = U, Np) chlorido-ketoenaminate complexes of the type [AnCl₂(TFB-tBuA)₂(THF)] (An-1 type: U-1, Np-1; TFB-tBuA = 4-(tertbutylamino)- 1,1,1-trifluorobut-3-en-2-one) and the homoleptic Np^IV heteroarylalkenolate complexes [Np(PyTFP)₄] (Np-2, PyTFP = 1-(pyridin-2-yl)-3,3,3-trifluoroprop- 1-en-2-ol) and [Np(DMOTFP)₄] (Np-3, DMOTFP = 1-(4,5-dimethyloxazol- 2-yl)-3,3,3-trifluoroprop-1-en-2-ol) were synthesized and characterized (SC-XRD, NMR, Vis-NIR, MS). While their solid-state structures compare well to those of their uranium analogues, the behavior in solution showed significant differences. The binding motif of the DMOTFP ligand in complex Np-3 can change to form two different complex isomers, as seen by paramagnetic chemical shifts in NMR experiments. Furthermore, the flexibility and the influence of the steric effects at the N-side of the ligands are discussed and compared with its uranium counterpart.

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Research Organization:: Colorado School of Mines, Golden, CO (United States); Helmholtz-Zentrum Dresden-Rossendorf (Germany); University of Cologne (Germany)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0023693

OSTI ID:: 2507103

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 5 Vol. 64; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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